- 


ISOCAMPHOLACTONE 

BY 

PHILIP  KELSEY  PORTER 
A.  B.  Grinnell  College,  1918 


THESIS 

Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 

Degree  of 

MASTER  OF  ARTS 
IN  CHEMISTRY 

IN 

1 HE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 


1921 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


THE  DEGREE  OF_ 


Recommendation  concurred  in* 


ART' 


In  Charge  of  Thesis 


hjead  of  Department 


Committee 


on 


Final  Examination* 


*Required  for  doctor’s  degree  but  not  for  master’s 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/isocampholactoneOOport 


TABLE  OP  CONTENTS 


Page 

IlfBOLUCTIOH  1 

THE 0 SET I GAL  P^HT  3 

Eii.PEHIi-.iGi:  TAL  PART 

Preparation  of  Camphoric  Acid  6 

Preparation  of  Camphoric  Anhydride  6 

Preparation  of  Alpha  and  Beta  Camphoramidic  Acids  6 

Preparation  of  Amino  Lauronic  acid  7 

Preparation  of  the  Anhydride  and  the  i. itroso 

Leri-fat  ive  of  .amino  Lauronic  Acid  8 

Preparation  of  Iso-campholactone  10 

Preparation  of  h it ro- iso-campholactone  11 

Preparation  of  Camphoric  Imide  11 

Attempted  Preparation  of  and  Camphoramidic 

Acids  from  Camphoric  Imide  12 

A CEli  OviojjjU  Gni.u'ii'-i  T 


IL 


loU  C.hvn . IQ  LAG  'I  Oh  A 


I BllHQDUCTIOii 

Camphor  and  its  derivatives  aiten  undergo  molecular  r car range - 
Very  little  is  known  conoemii 
re  ri  - jement , — it  is  often  extremely  difficult  to  'de 

whether  a rearrangement  has  t.  men  place  in  a given  reaction  or  not 
The  first  step  in  determining  whether  a rearrangement  has  t; .ken 
place  is  to  prove  the  structure  of  the  compound  resulting  IroQi 

- - This  : iffj  one  must  use  a 

sort  of  cumulative  evidence,  which  is  obtained  from  a study  of  the 
reactions  c lpo  oft  . 

fhe  study  of  the  derivatives  of  camphor  give  many  examples  of 
bs . ...  - i oso  of  the 

amino  lauronic  acid  is  treated  with  sodium  hydroxide , laurolene  is 
formed  as  one  of  the  products."1 


rip  -4-  C 0 , -f-  i; 
/ . * 


Lu  ibis  reaction,  nyl  and  amino  groups  leave  the  molecule 

as  carbon  dioxide  and  nitrogen,  . 1 group  shifts  to  form 

t . ie  1 , 2 , 6 , t rime thyl  c onnound  . 

In  the  same  . hon,  isocampholactone  is  formed.  As  the 
structure  ox  this  compound  has  not  been  j roven , there  is  a strong 

possibility  that  another  type  of  rearrangem  t n pi  ce. 

The  o eject  of  this  work  was  to  continue  the  study  of  the  reactions 


1 


tloyes  and  Derick,  J.ADhe  . . .. . 1,- 


. 


. 

. 

, . 


. . 


» ■ os s ible , 

ossifole  structure  of  the  compound,  and  nature  of  the  rearrangement* 
is  taken  place • 

veiy  little  progress  toward  the  study  of  the  larger  question  in 

» nP-  e • However,  the  series  oi  reactions 

wilioil  ±'^L  to  tiie  prepar  it  ion  f isooampholactone  have  keen  studied, 
and  in  Most  cases,  an  increase  in  yields  have  "been  obtained  "by 
— l j g ei one r tne  uet.ioes  that  have  "been  described,  or  by 
Ge  -*  oc In  ...  s « 


TjA0&3TIG.ii  1AAT 

Three  laetones  are  known  which  correspond  to  three  hydroxy 
a°i^s  - - - the  tertiary  carboxyl  of  camphoric  acid.  They 

are  the  campho  lac  tone , the  cis-ca  ij  nololactone,  and  the  iso- 

\ 

campholact one . 

Campholactone  was  first  prepared  by  fitting  x_d  Wor L.iger-'-  by 
warming  lauronolic  acid  with  dilute  mineral  acid.  It 

Soyes  ■ - Si  thio  let  od . laurolene 

1 also  beeix  prepares  oy  the  distillation  of  lanronolic  acid*^, 

. shifting  of  the  methyl  group  to  the  1,2,3,  trimethyl  com- 

pound may  nave  occurred  either  during  the  formation  of  lauronolic 
acid  or  during  its  decomposition  to  form  laurolene.  The  experiment- 
al woik  ui  i.oyes  ana  nurne"  snows  tnat  the  shift  oi  the  methyl  gr quo 
tcxw.es  place  in  tne  formation  of  lauronolic  acid.  This  gives  the 
structure  of  campholactone  as  being  formed  by  a rearrangement  of 
kke  methyl  groups  giving  the  1,2,3  t rime thy 1 compound.  Its 
structure  may  ue  represented  ,y  the  following  formula. 


GHr 


he; 


Hw 
CK^ 


'31  ft 


u 


GH-G- 


GH2 


-GH, 


Cis-camphonololactone  was  first  obtained  by  lioyes  and  Taveau4 , 
who  decomposed  the  nitroso  derivative  of  the  anhydride  of  amino 
lauronic  acid  by  warming  it  with  a 10?o  solution  of  iiaOE.  Bredt^ 

^fitting  and  .'oringer.  Aim.  227,-10 
TJioyes  mid  Burke,  J.n.G.8.  34,-182 
^..alker  and  Henderson?  J.  Ghem.  hoc.  69,-749 
floyes  and  Teveau,  am.  Ghem.  J.  35,-385 
° 3r edt , Ann . 561,-1 


-4- 


later  prepared  it  by  the  electrolytic  reduction  of  Camphononic  acid. 
The  structure  of  camphononic  acid  has  been  shown  by  Lapworth  and 


tion  of  camphononic  acid,  the  cis-campholic  acid  is  formed,  which 
upon  heating  gives  the  cis-camphonololactone . This  lactone  has 
been  oxidized  back  to  t c mj  . This  series  of  reac- 

tions show  that  cis-camphonololactone  is  formed  with  no  molecular 

ment , and  its  structure  may  be  represented  by  the  following 


Iso campholac tone  is  the  third  3 . known,  which  retains 

the  tertiary  carboxyl  of  camphoric  acid*  It  was  first  obtained  by 
the  action  of  nitrous  acid  on  amino  lauronic  acid.  It  was  later 


who  made  a further  study  of  the  lactone. 

The  structure  of  this  lactone  has  not  been  proven  and  it  is 
still  open  to  question.  The  possibility  of  a more  complicated 
rearrangement  in  the  formation  of  the  lactone  Is  entirely  probable. 

Isoc  iphol  3tone  has  been  oxidized  by  nitric  acid,  which  form- 
ed as  the  principle  product  , the  nitro-iso-campholact'one 
CJgH^  (UO  ,\^|  and  also  an  acid  GgH^gO^,  mel  ...  at  I.  . The 
titration  with  standard  alkali  against  t .is  acid  gave  results  cor- 
responding to  the  molecular  weight  of  186D  and  186.9  for  a monobasic 

Is  le  , o • Chem.  ooc . 79 ,— l^of 


lent  on1  to  consist  of  ±±o  molecular  rearrange  mu.  t . By  the  reduc- 


anhydride  of  amino lauronic  acid  with  sodium  hydroxide . This 
method  was  repeated  by  loyes  and  Taveau®  and  by  fcoyes  and  Homberger^ 


cLt  , B . 
3n  oyes  and 


,-l 


niveau 


G.J 


, 


■ t 

. . 


-5- 


acid.  . . do  s a lactone  group,  was  s 

ing  a portion  of  it  in  a sealed  tube  with,  an  excess  of  sodium 

hydroxide.  .056$  ms  of  the  acid  neutralized  6.57  cc.  of  L/iC 

BaOH , the  calculated  amount  for  a dibasic  acid  being  6. 18  cc. 

The  barium  salt  and  the  amide  were  als(  ..... 

The  nitro-iso-campholactone  was  reduced  1 . e amino-iso- 

campholac t one  (inig )\^y0  and  also  the  hydroxylaminoisocampho- 

0 

lactone,  G . 

0 

Perhaps  the  most  interesting  reaction  in  the  study  of  this 

compo , is  ...  jomj  si  ion  of  the  nitroisocampholactone  by 

ionium  hydroxide,  and  sodium  hydroxide  to  form  compc 
. ....  ion  atoms  ....  molecule  ’while  carbon  dioxide  is  given  off. 

Upon  warming  the  nitre  lactone  with  alcoholic  ammonia  or  on  treat- 
ment with  cold  concentrated  aqueous  ammonium  hydroxide,  the  amide 

is  f , wh ..  ...  . lpiri  1 , 

.....  .....  i s saponified  th  .514  BaOH,  giving 

an  acid  melting  .t  75° 0. 

Upon  treating  the  nitroisocamphol:  ctcne  directly  with  .5B 

BaC  , car  on  dioxide  ia  given  off,  and  upon  acidifying,  an  acid  was 

/ 

obtained,  which  was  identical  with  the  acid  obtained  from  the  amide. 
Titration  o_  . lie  i B/lO  BaOH  gave  a molecular  weight  of 
162.$  163 , ...  n 'v  _ xide  gave  166 . The 

theoretical  molecular  weight  foi  3 eing  159. 

a further  study  of  these  compounds  may  throw  some  light  upon 
the  robable  structure  cl  the  lactone. 


. 


, 


■ 


— u — 


X O 0 pa  xa  t X OJL.  a-  Xx^.-xpl'l  0 1'  j b AiO  j-U.  « 

JaiUpilO  n G UCie.  VicxS  p 37t.  pc-l’C  d.  ck>^  bOx'dx..ug  to  me  ...1C  1>-1CU  C-S  u 6SCn  u — 

-} 

...  3 , ] ... 

mother  liquor , which  gave  a decrease  in  the  yield  , or  4 p theoreti- 
cal . 

xiie  v/ o x v xuj.t  i ii’  t.ire e circle;,  L j. u*. & vuxxSu  j — o...  oi  uO  6G’/v 

ore , -v  . Lai  ..  ies  c i 

were  oxidized  at  a tine,  and  the  sane  results  were  obtain  d. 

■X  X-* o .ja  x . .I  uX  OX  sXC-l.l  . O w » 


Campnonc  anhydride  was  1 re  pared  ac  «. o x’d  ixig  to  Ixr  e i.*e  xic  u &s 


described  b.y  Loye 


.,1 


_ . ger  quantities,  as  5QC 


acio. , were  used  at  Ox^e  ti  e , < .nd  is  sjc  i s ..  — oox  ... 

file  yields  varied  iron  66  to  93c/o  theoretical , with  an  average  of 

9 0 yo . 

... ...  . i on  — 0.  | .....  j . 03  ii  . ...  Acic  . • 

the  alpha  and  beta  campho  rami  die  acids  were  prepared  according 

s de s crib  y 1 . . i 5 of 

camphoric  anhydride  were  treated  with  6c  cc.  co...  cent  rated  a. .non  run 

hy  dro — Lde  , 1 . cc  * wa fc . ..  — ..  pressure  bottle  • dhe  bottle 

was  wrapped  in  a towel , and  shaken  for  ten  minutes,  after  which 

it  was  placed  In  a 3ol  ....  h,  an  _ dually  heated , shaking 

' it  occasionally  . A pi  ic  llj  1 . 

\ 

After  cooling  somewhat,  the  cent  exits  in  the  bottle  were  poured  into 
a 3eaker,  jooI  Ly  s po  constant  stirring. 

I L€  . . id  crystallized;  out  ux.d  was  filter- 


Loyes , .A*C.*L  16,-501,  502 
2ivoyes  ud  faveau,  .a.  5.  J-,  52,-285 


. 


* ’ * • ' * 

.... 


-7- 


I ..  y recryg  .lizat  a small 

of  warm  water  and  ammonia. 

The  filtrate  i'r. • m the  alpha  salt  contained  the  salt  of  the 
beta  acid.  To  this,  30  go.  of  sodium  hydroxide  (3  cc.  = 1 gram.) 
were  added,  with  stirring,  and  the  sodium  salt  of  the  beta  acid 
was  precipitated.  The  filtrate  from  this  solution ,• and  the  mother 
liquors  from  the  purification  of  the  alpha  salt  were  carefully 
neutralized  with  hydrochloric  acid.  30]  s constantly 

stirred,  and  the  acid  added  very  slowly  until  the  mixed  acids  be- 
gin to  separate  out  as  a crystalline  product.  The  addition  of 
a small  amount  of  some  mixed  acids  from  a previous  preparation  may 
preTi  nt  the  precipitation  of  the  acids,  as  a gummy  product.  The 
acids  were  filtered , and  then  dissolved  in  a little  more  than  the 
theoretical  amount  of  ammonium  hydroxide  and  the  separation  repeat- 
ed. 

To  obtain  the  free  amidic  acids,  the  ammonium  or  sodium  salt 
was  dissolved  in  water,  and  concentrated  hydrochloric  acid  was 
added,  using  the  same  precautions,  to  insure  a crystalline  product 

. The  yields  varied  from  55  to  65'/U  by  weight  of  the 

alpha  salt,  and  from  Os  to  68 $ of  the  beta  salt.  Precipitation 
of  the  acids  from  the  salts  gave  yields  varying  from  75-78$  of  the 
alp  la  ci  , md  from  50-55$  of  the  beta  acid.  The  yields  of  acids 
based  upon  the  amount  of  camphoric  anhydride  used,  gave  from  45-50$ 

ight  of  e al] acid,  c 35-45;  of  the  beta  acid. 

Preparati  on  of  „n,iino  fauronic  ^cid . 

Amino  lauronic  acid  was  prepared  according  to  the  method  as 

1 

described  by  hoyes  # 199  grams  (1  mole)  of  the  alpha  acid  were 

-1-  hoyes, 


. A . C . J . 16,-506 


J 


-8- 


dissolved  in  a liter  of  a 10$  solution  of  IJ'aOH.  51  go.  or  160  g. 
of  bromine  were  dissolved  in  1100  cc.  of  a 10$  solution  of  II  a OH, 

ana  this  solution  of  hypobromite  ac.de d to  the  solution  of  the  alpha 

c 

acid.  The  solution  was  ieai  . water  bath  to  about  75  for 

os.  After  cooling,  a little  sodium  sulfite  was  added, 
and  the  solution  was  strongly  acidified  with  HOI.  The  solution 
was  then  porated,  and  the  amino  acid  separated  out  as  the  hydro- 
Ohio ride , and  may  be  purified  by  a re-  lizati  i r. 

The  yield  was  about  100$  theoretical. 

Preparation  of  t..e  .niliydride  a^o  the  nit, oso  Derivative 
of  nmiiiQ  rauronic  ^cid . 

The  anhydride  of  amino  lauronic  acid  has  been  prepared  by  the 
following  methods;  by  distilling  the  hydrochloride  of  amino  lauron- 
ic acid  with  an  excess  of  lime^;  by  heating  the  free  amidic  acid 
to  300° in  an  oil  bath  ; by  heating  the  hydrochloride  with  acetic 

a 

anhydride^;  and,  by  heating  the  hydrochloride  with  acetic  anhydride 

4 : 

and  fused  sodium  acetate  . From  all  of  these  methods,  the  nitroso 

derivative  was  obtained  by  dissolving  the  anhydride  in  dilute  EG1 

and  adding  sodium  nitrite. 

All  of  these  methods  were  tried,  with  varying  yields  of  nitroso, 
However,  it  was  thought  best  to  unite  these  two  reaction,  and  not 
is olal  pur  ydride , was  done  as  fai  as  possible. 

Dive  and  two  tenths  grams  of  the  free  acid  were  heated  in  a 
•< oo<~  1 metal  ba  i at  300°  fox  one  lour.  The  at  lydride  formed  was 
dissolved  in  ether  and  the  ether  distilled  off.  The  impure  anhy- 
dride was  then  dissolved  in  dilute  HC1,  and  so  .1  uni  nitrite  added. 


1 


Doyes,  16,-507 

%loyes  and  lave au , <A. • 0. . J. 


A ft 

1-1  •.  ->  • 


32,-287 


SBredt , 3.  35,-1251 


■ 


. 


. 


* 


. 


t 


. , 


* 

..... 


-9- 

.638  grama  of  the  iiitroao  derivative  were  obit , or  12$  by 

weight  from  the  amount  of  amino  lauronic  acid  taken. 

rive  and  two  tenths  grams  of  the  hydrochloride  with  10  cc . of 
acetic  anhydride  and  2 grams  of  f sed  sodium  acetate  were  heated 
2 hours  over  a very  small  flame . The  anhydride  was  obtained  by 
extrac  ith  her.  It  was  then  dissolved  in  dilute  HC1,  and 

sodium  nitrite  added.  2.066  grams  of  the  nitroso  derivative  were 
obtained,  or  40$  yield  by  weight . 

Five  and  two  tenths  grams  of  the  hydrochloride  and  11  grams  of 
lime  were  heated  in  a Wood’s  metal  bath  for  one  and  one -half  hours 
at  a temperature  of  280°.  The  mass  rac . ic . fch  not 

water,  filtered,  acidified  with  [Cl,  cc  dI  , and  sodium  nitrite  . 
ad  3d.  2.226  grams  of  the  nitroso  derivative  were  obtained,  or  a 

yield  of  43$  by  weight. 

It  was  founc  however,  that  by  distilling  a mixture  of  the 


h .ro chloride  and  calcium  carbonate  instead  of  lime,  better  yields 
than  those  from  the  other  method  were  obtained. 

Twenty  grams  of  the  hydrochloride  and  40  grams  of  calcium 
cai  ...  .....  mixec  , < ...  ..  t.  ...  mass 

heated,  quite  strongly  with  a free  fl  me.  The  anhydride  formed, 


was  distilled  over  into  a flask  cooled  by  ice  water,  or  it  sublimed 
in  the  neck  of  the  retort.  The  heating  was  continued  for  about 

one-half  Lour,  oi  - all  of  ...  anhyc  had  distilled,  or  sub- 

limec  . on  cooling,  the  anhy  ide  3 ...ass  in  the  retort 

were  extracted  throe  times  with  hot  water,  fcered,  1 te  an- 
hydride being  soluble  in  water.  The  filtrate  was  acidified  with 

i-.'j.L  ex  rid  coomed.  6c  ...  ..  .....  .0  added  witn  constant  st_ . , 


-10- 


to  insure  the  precipitation  oi  the  nitroso  as  a crystalline  product. 

It  was  sometis.es  necessary  to  inoculate  the  solution  with  some 

, t o prevej  of  i inmy 

md  less  pure  compound . The  nitroso  derivative  was  purified  by 

0 0 

crystallizing  once  from  alcohol.  It  melts  at  158-139  J. 

Ihe  yields  varied  from  10.5  grams  so  one  high  yield  of  15.8  g. 
which  was  an  average  yield  of  11.5  grams  or  66,.  theoretical  from 

amino  1 3 n. 

Preparation  or  Iso-camphoiactone . 


iso-cam  - pared  by  the  method  as  c . . 

hoyes  and  Taveau  using  a log  solution  of  baOh,  anc  also  by  the 
method  as  described  by  boyes  and  Potter2  in  their  preparation  of 
. is  — c phono lol  Lone , - - , - — - I ...  • 

modification  made  in  their  method  was  the  fact  that  after  distilling 
off  the  laurolene , the  solution  was  made  acid,  and  steam  distilled 
directly  without  extracting  the  acids  and  lactones  with  ether. 

Due  to  t e fact  .hat  the  cis-camj  lonolol  . . . . was  also  prepared , 
perhaps  by  the  use  of  the  stronger,  sodium  hydroxide,  and  the  higher 
. i]  --  ;ure  Cc  nod  by  the  heat  of  reaction,  and  being  somewhat  vola- 
tile ...  .-v  am,  a mixture  of  the  two  1 .so tw.es  were  obtained. 

These  separated  by  refluxi  g the  lactones  with  a 5p  solution  of  LaGH 

for  3C  . s , 1 i€  . ..  -c  lolactone , 

of  the  isocampholaot one . Ihe  solution  was  cooled  to  zero  degrees 


and  acidified,  separati:  '.he  isocsmpholactone  and  the  ..._  Lroxj 

acid  corresponding  to  the  cis-camphonololactone . These  were  ex- 


. oy e s - . , l. *.G  ..I*.  32 , — ! 

8h  ^ . Pott  ■.  . . . •>  • b . , — ^ 


' 


-11- 

traoted  with  ether,  and  the  other  distilled  off  under  diminished 
pressure  so  as  to  keep  the  temperature  low.  The  hydroxy  as  id 
was  tnen  dissolved  ixx  a i^o  .assrum  carGOxxate  solution,  and  ^..o  iso— 
oampholao tone  was  purified  by  distillation  under  diminished  pressure 
The  boiling  point  of  the  is ooampholactone  was  121-122°  at  25 

O O 

mm.  pressure,  and  the  ...  . oi  -32  . 

about  20$  by  we.. . . mount  of  x.itroso  derivative  taken. 

irrupt  rat  i Oxx  or  i itro-J-aoca.-i^olactoxie  . 
Nitro-isocampholactone  was  prepared  according  to  the  method  as 
icr:  Noyes  . . 2.031  grams  of  the  isocampho- 

lactoxie  axid  5 cc . of  nitric  acid  (sp.  gr.  1.27)  were  refluxed  in  a 
5s  so.  flask  . 56  hours  over  a steam  bath,  until  the  oily  layer 

of  lactone  disappeared,  a little  concent  rated  acid  being  added  from 
time  to  time.  Upon  cooling  and  dilution  with  water,  the  nitro- 
is ooampholactone  crystallized  out.  1.2  grams  of  the  nitro  lactone 
were  obtained  , m 121-122,  yield  of  46  fo  theoretical. 

-reparation  p__  Jam:.horic  Imide  . 

ms  of ^-camphoramidic  acid  and  IGOcc.  of  concentrated 

. 31  and  25  co . of  wg  fl  ours 

The  solution  coolec  and  who  imide  filtered  c The  im- 

p imide  by  dissolving  it  in  2ou  cc.  of  a 5$  solution 

of  laOH,  axid  r e p r e c ip) i t a t in g it  by  passing  a strong  current  of  OOg 
hro  olution.  iel  ..  ...  72$  theoretical. 

It  melts  at  245° . 

The  filtrate  from  the  camphoric  imide  gave  a precipitate  oi 
camphoric  acid  'when  acidified  with  HOI . An  attempt  was  made  to 
inn  >f  ; acid  od. 

1 Noyes  and  iiomberger,  J.A.G.a.  31,-280 


. ti 


-12- 

However , no  imide  wa  obtained,  but  c . ..  ..  ric  cic  pre- 

3o , is  of  both,  the  D(  and  P-camphor- 

ami arc  a c i 0.  s uO  campho x i o a c i 0.  * . a a 0 b c e d oy  bet x'lmxi . x*e  a — 
mounl  ion  c in  the  it  ion. 

1.0012  grams  of  fr(-c  mphoi Lc  . 2 cc.  of  03  3 

HC1 , and  .5  cc.of  ws  1 3 re  re on  a water  bath  for  £4  hours. 

The  solution  was  t _en  slowly  evaporated  to  dryness  on  a water  bath, 
and  the  residue  extracted  with  water  to  dissolve  the  ammonium 
chloride  formed  by  the  rol  ,.  the  solution  was  diluted  to 

..  cc*  fr< Jh  ire  samples  of  2C  cc.  each  were  pipetted  off,  and 

an  excess  of  sodium  carbonate  added  to  each  sample.  Air  was  pass- 
ed through  the  solution  for  three  hours,  drawing  the  ammonia  into 
standard  acid,  nd  he  excess  acid  titrated  with  st  li. 

She  two  samples  were  equivalent  io  14.9  and  15.005  cc.  of  .0924  3 
acid  respectively , or  the  total  volume  of  50  cc.  of  solution  was 
equivalent  to  37.53  cc.  of  aci  . This  being  equivalent  to  .18478 
grams  of  amrnoi  e 68.64$  of  the  acid  is  hydro- 

lysed to  camphoric  acid. 

Five  grams  of  the  ^*camphoramidic  o.cid  7/e  re  treated  in  like 
man  1 a s K-  id.  The  tw<  mj  3 20cc.  each  we  re  e 3 nt 

to  14.11  cc.  and  14.28  cc.  of  .0924  3 acid  respectively,  or  the 
total  volume  of  50  cc.  was  equivalent  to  35.5  cc.  of  acid.  This 
bei  equivalent  to  .1775  grams  of  ammonium  chloride , shows  that 
13.2$  the  (3-acid  is  hydrolyse  . A second  determination  was  made 
in  the  same  manner , and  14.4$  of^-acid  was  fc  me  :o  be  hydrolysed. 
attempted  a rep-  ration  of  fthnd  ^Ouu.  hora.nii  ic 
-xcids  from  Camphoric -imide  . 

Twenty  five  grams  of  the  imide  were  dissolved  in  80  cc.  of 


-13- 


15%  KaOH  and  the  solution  was  heated  on  a water  "bath  for  one  and 
one-half  hours.  On  cooling  and  adding  a crystal  of  some  /3-salt, 
the  sodium  salt  separated  and  filtered  off.  salt  was  dissolv- 

j;  , e/5-acid  _ ...  cipitated  bj  HG1.  THe  yield  is 

about  14-15  grams  of  /5-acid.  She  alkaline  mother  liquor  was  acidi- 

fied with  HC1 , in  hopes  of  obtaining  some  impure  (K~ac id , but  none 
was  obtained.  The  possibility  of  a further  hydrolysis  to  camphor- 
ic acid  will  be  studied  later. 


xLOKL'i  0 w jjHj  jjGriiijiitjii.  x 

xhe  writer  wishes  to  express  his  thanks  to  Doctor  william  n. 
Doyes  for  the  many  valuable  suggestions  in  connection  with  this 
investigation. 


